Chapter 3: The Structure of Crystalline Solids

ISSUES TO ADDRESS...
• How do atoms assemble into solid structures?
(for now, focus on metals)

• How does the density of a material depend on

its structure?

• When do material properties vary with the

sample (i.e., part) orientation?

Chapter 3 - 1
 Energy and Packing
• Non dense, random packing Energy

typical neighbor
bond length

typical neighbor r
bond energy

• Dense, ordered packing Energy

typical neighbor
bond length

typical neighbor r
bond energy

Dense, ordered packed structures tend to have

lower energies.
Chapter 3 - 2
 Section 3.3 – Crystal Systems
Unit cell: smallest repetitive volume which
contains the complete lattice pattern of a crystal.

7 crystal systems

14 crystal lattices

a, b, and c are the lattice constants

Fig. 3.4, Callister 7e.

Chapter 3 - 4
Crystal Systems

Chapter 3 - 5
Section 3.4 – Metallic Crystal Structures
• How can we stack metal atoms to minimize
empty space?
2-dimensions

vs.

Now stack these 2-D layers to make 3-D structures

Chapter 3 - 6
 Metallic Crystal Structures
• Tend to be densely packed.
• Reasons for dense packing:
- Typically, only one element is present, so all atomic
radii are the same.
- Metallic bonding is not directional.
- Nearest neighbor distances tend to be small in
order to lower bond energy.
- Electron cloud shields cores from each other
• Have the simplest crystal structures.
We will examine three such structures...

Chapter 3 - 7
 Simple Cubic Structure (SC)
• Rare due to low packing denisty (only Po has this structure)
• Close-packed directions are cube edges.

• Coordination # = 6
(# nearest neighbors)

(Courtesy P.M. Anderson)

Chapter 3 - 8
 Atomic Packing Factor (APF)
Volume of atoms in unit cell*
APF =
Volume of unit cell
*assume hard spheres
• APF for a simple cubic structure = 0.52
volume
atoms atom
a 4
unit cell 1 (0.5a) 3
3
R=0.5a APF =
a3 volume
close-packed directions
unit cell
contains 8 x 1/8 =
1 atom/unit cell
Adapted from Fig. 3.23,
Callister 7e. Chapter 3 - 9
Body Centered Cubic Structure (BCC)
• Atoms touch each other along cube diagonals.
--Note: All atoms are identical; the center atom is shaded
differently only for ease of viewing.

ex: Cr, W, Fe (), Tantalum, Molybdenum

• Coordination # = 8

Adapted from Fig. 3.2,

Callister 7e.

2 atoms/unit cell: 1 center + 8 corners x 1/8

(Courtesy P.M. Anderson)
Chapter 3 - 10
 Atomic Packing Factor: BCC
• APF for a body-centered cubic structure = 0.68
3a

2a

Close-packed directions:
R length = 4R = 3 a
Adapted from
Fig. 3.2(a), Callister 7e.
a
atoms volume
4
unit cell 2  ( 3a/4 ) 3
3 atom
APF =
3 volume
a
unit cell Chapter 3 - 11
 Face Centered Cubic Structure (FCC)
• Atoms touch each other along face diagonals.
--Note: All atoms are identical; the face-centered atoms are shaded
differently only for ease of viewing.
ex: Al, Cu, Au, Pb, Ni, Pt, Ag
• Coordination # = 12

Adapted from Fig. 3.1, Callister 7e.

(Courtesy P.M. Anderson)

4 atoms/unit cell: 6 face x 1/2 + 8 corners x 1/8
Chapter 3 - 12
 Atomic Packing Factor: FCC
• APF for a face-centered cubic structure = 0.74
maximum achievable APF!
Close-packed directions:
length = 4R = 2 a
2a
Unit cell contains:
6 x 1/2 + 8 x 1/8
= 4 atoms/unit cell
a
Adapted from
Fig. 3.1(a),
Callister 7e. atoms volume
4
unit cell 4 ( 2 a/4) 3
3 atom
APF =
volume
a3
unit cell
Chapter 3 - 13
 FCC Stacking Sequence
• ABCABC... Stacking Sequence
• 2D Projection
BB BB
C
A
A sites BB BB BB
C C
BB sites
sites BB BB
C sites

A
• FCC Unit Cell B
C

Chapter 3 - 14
 Hexagonal Close-Packed Structure
(HCP)
• ABAB... Stacking Sequence
• 3D Projection • 2D Projection

A sites Top layer

c
B sites Middle layer

A sites Bottom layer

a Adapted from Fig. 3.3(a),
Callister 7e.

• Coordination # = 12 6 atoms/unit cell

• APF = 0.74 ex: Cd, Mg, Ti, Zn
• c/a = 1.633 Chapter 3 - 15
 Theoretical Density, 

Mass of Atoms in Unit Cell

Density =  =
Total Volume of Unit Cell

nA
 =
VC NA

where n = number of atoms/unit cell

A = atomic weight
VC = Volume of unit cell = a3 for cubic
NA = Avogadro’s number
= 6.023 x 1023 atoms/mol

Chapter 3 - 16
 Theoretical Density, 
• Ex: Cr (BCC)
A = 52.00 g/mol
R = 0.125 nm
n=2
R
a a = 4R/ 3 = 0.2887 nm

atoms
g
unit cell 2 52.00 theoretical = 7.18 g/cm3
mol
= actual = 7.19 g/cm3
a3 6.023 x 1023
volume atoms
unit cell mol Chapter 3 - 17
 Densities of Material Classes
In general Metals/
Graphite/
Composites/
metals > ceramics > polymers Alloys
Ceramics/
Semicond
Polymers
fibers
30
Why? Platinum
Based on data in Table B1, Callister
*GFRE, CFRE, & AFRE are Glass,
20 Gold, W
Metals have... Tantalum Carbon, & Aramid Fiber-Reinforced
Epoxy composites (values based on
• close-packing 60% volume fraction of aligned fibers
10 Silver, Mo in an epoxy matrix).
(metallic bonding) Cu,Ni
Steels
• often large atomic masses Tin, Zinc
Zirconia

 (g/cm3 )
5
Ceramics have... 4
Titanium
Al oxide
Diamond
• less dense packing 3 Si nitride
Aluminum Glass -soda Glass fibers
• often lighter elements Concrete
Silicon PTFE GFRE*
2
Polymers have... Magnesium Graphite
Silicone
Carbon fibers
CFRE*
Aramid fibers
PVC
• low packing density PET
PC
AFRE*
1
(often amorphous) HDPE, PS
PP, LDPE
• lighter elements (C,H,O)
0.5
Composites have... 0.4
Wood

• intermediate values 0.3

Data from Table B1, Callister 7e.
Chapter 3 - 18
 Single Crystals
• For a crystalline solid, when the periodic
and repeated arrangement of atoms
extends throughout without interruption,
the result is a single crystal. Huge KDP (monopotassium phosphate)
crystal grown from a seed crystal in a
• The crystal lattice of the entire sample is supersaturated aqueous solution at LLNL.
Below, silicon boule.

continuous and unbroken with no grain

boundaries.
• For a variety of reasons, including the
distorting effects of impurities,
crystallographic defects and dislocations,
single crystals of meaningful size are
exceedingly rare in nature, and difficult to
produce in the laboratory under controlled
conditions.
Chapter 3 - 19
 SINGLE CRYSTALS

Garnet single crystal from China

Ruby crystals from
Pyrite (FeSTanzania
2) (Fool’s Gold) crystals from Spain Chapter 3 -
 Crystals as Building Blocks
• Some engineering applications require single crystals:
--diamond single --turbine blades
crystals for abrasives Fig. 8.33(c), Callister 7e.
(Fig. 8.33(c) courtesy
(Courtesy Martin Deakins, of Pratt and Whitney).
GE Superabrasives,
Worthington, OH. Used with
permission.)

• Properties of crystalline materials

often related to crystal structure.
--Ex: Quartz fractures more easily
along some crystal planes than
others.
(Courtesy P.M. Anderson)

Chapter 3 - 21
 Polycrystals Anisotropic
• Most engineering materials are polycrystals.

Adapted from Fig. K,

color inset pages of
Callister 5e.
(Fig. K is courtesy of
Paul E. Danielson,
Teledyne Wah Chang
Albany)
1 mm

• Nb-Hf-W plate with an electron beam weld. Isotropic

• Each "grain" is a single crystal.
• If grains are randomly oriented,
overall component properties are not directional.
• Grain sizes typ. range from 1 nm to 2 cm
(i.e., from a few to millions of atomic layers).
Chapter 3 - 22
 Single vs Polycrystals
• Single Crystals E (diagonal) = 273 GPa
Data from Table 3.3,
-Properties vary with Callister 7e.
(Source of data is R.W.
direction: anisotropic. Hertzberg, Deformation
and Fracture Mechanics
-Example: the modulus of Engineering
Materials, 3rd ed., John
of elasticity (E) in BCC iron: Wiley and Sons, 1989.)

E (edge) = 125 GPa

• Polycrystals
-Properties may/may not 200 m Adapted from Fig.
4.14(b), Callister 7e.
vary with direction. (Fig. 4.14(b) is courtesy
of L.C. Smith and C.
-If grains are randomly Brady, the National
Bureau of Standards,
oriented: isotropic. Washington, DC [now
the National Institute of
(Epoly iron = 210 GPa) Standards and
-If grains are textured, Technology,
Gaithersburg, MD].)
anisotropic.

Chapter 3 - 23
 Section 3.6 – Polymorphism
• Two or more distinct crystal structures for the same
material (allotropy/polymorphism)
iron system
titanium
liquid
, -Ti
1538ºC
BCC -Fe
carbon
diamond, graphite 1394ºC
FCC -Fe
912ºC
BCC -Fe

Chapter 3 - 24
Allotropic Transformation

Chapter 3 - 25
 Section 3.8 Point Coordinates
z
111 Point coordinates for unit cell
c center are
a/2, b/2, c/2 ½½½

000
y
a b
Point coordinates for unit cell
x  corner are 111
z 2c


Translation: integer multiple of

  lattice constants  identical
b y position in another unit cell
b
Chapter 3 - 26
 Crystallographic Directions
z Algorithm
1. Vector repositioned (if necessary) to pass
through origin.
2. Read off projections in terms of
unit cell dimensions a, b, and c
y 3. Adjust to smallest integer values
4. Enclose in square brackets, no commas

x [uvw]

ex: 1, 0, ½ => 2, 0, 1 => [ 201 ]

-1, 1, 1 => [ 111 ] where overbar represents a
negative index
families of directions <uvw>
Chapter 3 - 27
 Linear Density
Number of atoms
• Linear Density of Atoms  LD =
Unit length of direction vector

[110]
ex: linear density of Al in [110]
direction
a = 0.405 nm

# atoms
a 2
LD   3.5 nm 1
length 2a

Chapter 3 - 28
 HCP Crystallographic Directions
z
Algorithm
1. Vector repositioned (if necessary) to
pass
through origin.
a2 2. Read off projections in terms of unit
cell dimensions a1, a2, a3, or c
- 3. Adjust to smallest integer values
a3
4. Enclose in square brackets, no commas
a2
a1 [uvtw]
a2 -a3
Adapted from Fig. 3.8(a), Callister 7e.
2

ex: ½, ½, -1, 0 => [ 1120 ] a3

a1
2
dashed red lines indicate
projections onto a1 and a2 axes a1
Chapter 3 - 29
 HCP Crystallographic Directions
• Hexagonal Crystals
– 4 parameter Miller-Bravais lattice coordinates are
related to the direction indices (i.e., u'v'w') as
follows.
z

[ u 'v 'w ' ]  [ uvtw ]

1
u (2 u ' - v ')
3
a2
1
v  (2 v ' - u ')
- 3
a3
t  - ( u +v )
a1
w  w'
Fig. 3.8(a), Callister 7e.

Chapter 3 - 30
Determining HCP Crystallographic
Directions

Chapter 3 - 31
Modulus Variation with direction

Chapter 3 - 32
 Crystallographic Planes

Adapted from Fig. 3.9, Callister 7e.

Chapter 3 - 33
 Crystallographic Planes
• Miller Indices: Reciprocals of the (three) axial
intercepts for a plane, cleared of fractions &
common multiples. All parallel planes have
same Miller indices.

• Algorithm
1. Read off intercepts of plane with axes in
terms of a, b, c
2. Take reciprocals of intercepts
3. Reduce to smallest integer values
4. Enclose in parentheses, no
commas i.e., (hkl)

Chapter 3 - 34
 Crystallographic Planes
z
example a b c
1. Intercepts 1 1  c
2. Reciprocals 1/1 1/1 1/
1 1 0
3. Reduction 1 1 0 y
a b
4. Miller Indices (110)
x
z
example a b c
1. Intercepts 1/2   c
2. Reciprocals 1/½ 1/ 1/
2 0 0
3. Reduction 2 0 0
y
4. Miller Indices (200) a b
x
Chapter 3 - 35
 Crystallographic Planes
z
example a b c c
1. Intercepts 1/2 1 3/4 
2. Reciprocals 1/½ 1/1 1/¾
2 1 4/3  y

3. Reduction 6 3 4 a b

4. Miller Indices (634) x

Family of Planes {hkl}

Ex: {100} = (100), (010), (001), (100), (010), (001)

Chapter 3 - 36
Crystallographic Planes

Chapter 3 - 37
 Crystallographic Planes (HCP)
• In hexagonal unit cells the same idea is used
z

example a1 a2 a3 c
1. Intercepts 1  -1 1
2. Reciprocals 1 1/ -1 1
1 0 -1 1 a2

3. Reduction 1 0 -1 1
a3

4. Miller-Bravais Indices (1011) a1

Adapted from Fig. 3.8(a), Callister 7e.

Chapter 3 - 38
 Crystallographic Planes
• We want to examine the atomic packing of
crystallographic planes
• Iron foil can be used as a catalyst. The
atomic packing of the exposed planes is
important.
a) Draw (100) and (111) crystallographic planes
for Fe.
b) Calculate the planar density for each of these
planes.

Chapter 3 - 39
 Planar Density of (100) Iron
Solution: At T < 912C iron has the BCC structure.
2D repeat unit

(100) 4 3
a R
3

Adapted from Fig. 3.2(c), Callister 7e. Radius of iron R = 0.1241 nm

atoms
2D repeat unit 1
1 atoms atoms
Planar Density = = 2 = 12.1 = 1.2 x 10 19

area a2 4 3 nm 2
m2
R
2D repeat unit 3
Chapter 3 - 40
The (111) plane of an BCC crystal structure

Chapter 3 - 41
 Planar Density of (111) Iron
Solution (cont): (111) plane 1 atom in plane/ unit surface cell

2a atoms in plane
atoms above plane

ni t
atoms below plane

tu
ea
rep
3
h a
2D 2
2
 4 3  16 3 2
area  2 ah  3 a  3 
2
R   R
atoms  3  3
2D repeat unit 1
atoms = atoms
Planar Density = = 7.0 0.70 x 1019
area 16 3 2
nm
2
m2
R
2D repeat unit 3
Chapter 3 - 42
 Section 3.16 - X-Ray Diffraction

• Diffraction gratings must have spacings comparable to

the wavelength of diffracted radiation.
• Can’t resolve spacings  
• Spacing is the distance between parallel planes of
atoms.
Chapter 3 - 43
DIFFRACTION

Chapter 3 - 44
 X-Rays to Determine Crystal Structure
• Incoming X-rays diffract from crystal planes.
de
te
c to reflections must
r be in phase for
a detectable signal
Extra distance
travelled
by wave “2” spacing
between
planes

Measurement of
critical angle, c,
allows computation of X-ray
intensity n
planar spacing, d. d
(from 2 sin c
detector)

c
Chapter 3 - 46
• X-rays are a form of electromagnetic radiation that have high energies and
short wavelengths—wavelengths on the order of the atomic spacings for
solids.
• When a beam of x-rays impinges on a solid material, a portion of this beam
will be scattered in all directions by the electrons associated with each atom
or ion that lies within the beam’s path.
• Bragg’s law, Equation 3.13, is a necessary but not sufficient condition
for diffraction by real crystals. It specifies when diffraction will occur
for unit cells having atoms positioned only at cell corners.
• d (hkl) = a / (h2 + k2 +l2)1/2 (Equation 3.14)
• However, atoms situated at other sites (e.g., face and interior unit cell
positions as with FCC and BCC) act as extra scattering centers, which can
produce out-of-phase scattering at certain Bragg angles.
• The net result is the absence of some diffracted beams that, according to
Equation 3.13, should be present. For example, for the BCC crystal
structure, h+k+l must be even if diffraction is to occur, whereas for FCC, h,
k, and l must all be either odd or even.

Chapter 3 - 47
Chapter 3 - 48
 Concept Check!

• For cubic crystals, as values of the planar indices h, k, and l

increase, does the distance between adjacent and parallel
planes (i.e., the interplanar spacing) increase or decrease?
Why?
• Answer: The interplanar spacing between adjacent
and parallel planes decreases as the values of h, k,
and l increase. As values of the planar indices
increase, the magnitude of the denominator
increases, with the result that the interplanar spacing
d (hkl) decreases.

Chapter 3 - 49
DIFFRACTION CONDITIONS IN FCC
& BCC

Atoms situated at sites other than cube corners act as

extra scattering centers, which can produce out-of-
phase scattering at certain Bragg angles.

The net result is the absence of some diffracted beams

that, according to Bragg’s equation, should be present. For
example, for the BCC crystal structure, h+k+l must be
even if diffraction is to occur, whereas for FCC, h, k, and l
must all be either odd or even.
Chapter 3 - 50
 X-Ray Diffraction Pattern
z z z
c c c

y (110) y y
a b a b a b
Intensity (relative)

x x x (211)

(200)

Diffraction angle 2

Diffraction pattern for polycrystalline -iron (BCC)

Adapted from Fig. 3.20, Callister 5e.

Chapter 3 - 51
 Sample Problem
• Interplanar Spacing and Diffraction Angle Computations
• For BCC iron, compute (a) the interplanar spacing, and (b) the
diffraction angle for the (220) set of planes.The lattice parameter for Fe
is 0.2866 nm. Also, assume that monochromatic radiation having a
wavelength of 0.1790 nm is used, and the order of reflection is 1.

Chapter 3 - 52
Chapter 3 - 53
 SUMMARY
• Atoms may assemble into crystalline or
amorphous structures.
• Common metallic crystal structures are FCC, BCC, and

HCP. Coordination number and atomic packing factor

are the same for both FCC and HCP crystal structures.
• We can predict the density of a material, provided we
know the atomic weight, atomic radius, and crystal
geometry (e.g., FCC, BCC, HCP).
• Crystallographic points, directions and planes are
specified in terms of indexing schemes.
Crystallographic directions and planes are related
to atomic linear densities and planar densities.

Chapter 3 - 54
 SUMMARY

• Materials can be single crystals or polycrystalline.

Material properties generally vary with single crystal
orientation (i.e., they are anisotropic), but are generally
non-directional (i.e., they are isotropic) in polycrystals
with randomly oriented grains.
• Some materials can have more than one crystal
structure. This is referred to as polymorphism (or
allotropy).
• X-ray diffraction is used for crystal structure and
interplanar spacing determinations.

Chapter 3 - 55